Photoinduced three-dimensional orientational order in side chain liquid crystalline azopolymers

We apply experimental technique based on the combination of methods dealing with principal refractive indices and absorption coefficients to study the photoinduced three-dimensional (3D) orientational order in the films of liquid crystalline (LC) azopolymers. The technique is used to identify 3D orientational configurations of trans azobenzene chromophores and to characterize the degree of ordering in terms of order parameters. We study two types of LC azopolymers which form structures with preferred in-plane and out-of-plane alignment of azochromophores, respectively. Using irradiation with the polarized light of two different wavelengths, we find that the kinetics of photoinduced anisotropy can be dominated by either photoreorientation (angular redistribution of trans chromophores) or photoselection (angular selective trans-cis isomerization) mechanisms depending on the wavelength. At the early stages of irradiation, the films of both azopolymers are biaxial. This biaxiality disappears on reaching a state of photosaturation. In the regime of photoselection, the photosaturated state of the film is optically isotropic. But, in the case of the photoreorientation mechanism, anisotropy of this state is uniaxial with the optical axis dependent on the preferential alignment of azochromophores. We formulate the phenomenological model describing the kinetics of photoinduced anisotropy in terms of the isomer concentrations and the order parameter tensor. We present the numerical results for absorption coefficients that are found to be in good agreement with the experimental data. The model is also used to interpret the effect of changing the mechanism with the wavelength of the pumping light.